Advances in Lithium-Ion Batteries

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Advances in Lithium-Ion Batteries

Edited by

Walter A. van Schalkwijk SelfCHARGE, Inc. Redmond, Washington Department of Chemical Engineering University of Washington Seattle, Washington, U.S.A.

and

Bruno Scrosati Department of Chemistry University of Rome “La Sapienza” Rome, Italy

KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW

eBook ISBN: Print ISBN:

0-306-47508-1 0-306-47356-9

©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©2002 Kluwer Academic/Plenum Publishers New York All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's eBookstore at:

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Acknowledgment

Dr. Scrosati would like to acknowledge his wife, Etta Voso, for her patience and continuous support of his work. The many exchanges with chapter authors were appreciated, as were the helpful suggestions of Mark Salomon. The contribution on fuzzy logic battery management from Professor Pritpal Singh of Villanova University and the rapid turn of some artwork by Liann Yi from his lab was greatly appreciated. Thank you also to Brad Taylor and Kevin Talbot for reworking some of the more complicated figures. Lastly, Dr. van Schalkwijk wishes to acknowledge the support of his co-editor, and the hospitality of his institution and research group during his visit to Rome. Walter van Schalkwijk Seattle, Washington Bruno Scrosati Rome, Italy

v

Contributors

Caria Arbizzani University of Bologna, Dip. Chimica “G. Ciamician”, Via F. Selmi 2, 40126 Bologna, Italy Doron Aurbach Israel

Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900,

George F. Blomgren Blomgren Consulting Services Ltd., 1554 Clarence Ave., Lakewood, Ohio 44107, U.S.A. Ralph J. Brodd Broddarp of Nevada, Inc., 2151 Fountain Springs Drive, Henderson, Nevada 89074, U.S.A. Michael Broussely

SAFT, F-86060 Poitiers, France

Robert M. Darling

International Fuel Cells, South Windsor, Connecticut, U.S.A.

John B. Goodenough Texas Materials Institute, ETC 9.102, University of Texas at Austin, Austin, Texas, U.S.A. Mary Hendrickson U.S. Army CECOM RDEC, Army Power Division, AMSEL-R2AP-BA, Ft. Monmouth, New Jersey 07703-5601, U.S.A. H. Ikuta Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku Tokyo 152-8552, Japan Minoru Inaba Department of Energy & Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan Hsiu-ping Lin MaxPower, Inc., 220 Stahl Road, Harleysville, Pennsylvania 19438, U.S.A. Marina Mastragostino University of Bologna, UCA Scienze Chimiche, Via San Donato 15, 40127 Bologna, Italy John Newman Department of Chemical Engineering, University of California at Berkeley; and Lawrence Berkeley National Labs, Berkeley, California, U.S.A. Yoshio Nishi Sony Corporation, 1-11-1 Osaki, Shinagawa-ku, 141-0032 Tokyo, Japan Zempachi Ogumi Department of Energy & Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan vii

viii

Contributors

Edward J. Plichta U.S. Army CECOM RDEC, Army Power Division, AMSEL-R2-APBA, Ft. Monmouth, New Jersey 07703-5601, U.S.A. Mark Salomon U.S.A.

MaxPower, Inc., 220 Stahl Road, Harleysville, Pennsylvania 19438,

Bruno Scrosati Department of Chemistry, University of Rome “La Sapienza”, 00185 Rome, Italy Francesca Soavi Univeristy of Bologna, UCI Scienze Chimiche, Via San Donato 15, 40127 Bologna, Italy Robert Spotnitz

Battery Design Company, Pleasanton, California, U.S.A.

Kazuo Tagawa Hoshen Corporation, 10-4-601 Minami Senba 4-chome, Chuo-ku, Osaka 542-0081, Japan Karen E. Thomas Department of Chemical Engineering, University of California at Berkeley; and Lawrence Berkeley National Labs, Berkeley, California, U.S.A. Y. Uchimoto Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku Tokyo 152-8552, Japan Walter A. van Schalkwijk SelfCHARGE, Inc., Redmond, Washington; and Department of Chemical Engineering, University of Washington, Seattle, Washington, U.S.A. M. Wakihara Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku Tokyo 152-8552, Japan Andrew Webber U.S.A.

Energizer, 23225 Detroit Rd., P.O. Box 450777, Westlake, Ohio 44145,

Jun-ichi Yamaki Institute of Advanced Material Study, Kyushu University, Kasuga 816-8580, Japan

Contents

Introduction B. Sacrosati and W.A. van Schalkwijk

1

1. The Role of Surface Films on Electrodes in Li-Ion Batteries

7

D. Aurbach

2. Carbon Anodes

79

Z. Ogumi and M. Inaba

3. Manganese Vanadates and Molybdates as Anode Materials for LithiumIon Batteries M. Wakihara, H. Ikuta, and Y. Uchimoto

4. Oxide Cathodes

103

135

J.B. Goodenough

5. Liquid Electrolytes J-i. Yamaki

155

6. Ionic Liquids for Lithium-Ion and Related Batteries

185

A. Webber and G. E. Blomgren

7. Lithium-Ion Secondary Batteries with Gelled Polymer Electrolytes

233

Y. Nishi

8. Lithium Polymer Electrolytes

251

B. Scrosati

9. Lithium-Ion Cell Production Processess

267

R.J. Brodd and K. Tagawa

10. Low-Voltage Lithium-Ion Cells

289

B. Scrosati

ix

Contents

x 11. Temperature Effects on Li-Ion Cell Performance M. Salomon, H-p. Lin, E.J. Plichta and M. Hendrickson

309

12. Mathematical Modeling of Lithium Batteries K.E. Thomas, J. Newman, and R.M. Darling

345

13. Aging Mechanisms and Calendar-Life Predictions M. Broussely

393

14. Scale-Up of Lithium-Ion Cells and Batteries R. Spotnitz

433

15. Charging, Monitoring and Control W.A. van Schlakwijk

459

16. Advances in Electrochemical Supercapacitors M. Mastragostino, F. Soavi and C. Arbizzani

481

Index

507

Advances in Lithium Ion Batteries Introduction Walter van Schalkwijk

Bruno Scrosati

SelfCHARGE Inc., Redmond, WA Department of Chemical Engineering, University of Washington, Seattle, WA USA

Universita "La Sapienza" Dipartimento di Chimica Opiazza Aldo Moro 5, 00185 Rome Italy

Portable power applications continue to drive research and development of advanced battery systems. Often, the extra energy content and considerations of portability have outweighed economics when a system is considered. This has been true of lithium battery technologies for the past thirty years and for lithium ion battery systems, which evolved from the early lithium battery development. In recent years, the need for portable power has accelerated due to the miniaturization of electronic appliances where in some cases the battery system is as much as half the weight and volume of the powered device. Lithium has the lightest weight, highest voltage, and greatest energy density of all metals. The first published interest in lithium batteries began with the work of Harris in 1958 [1]. The work eventually led to the development and commercialization of a variety of primary lithium cells during the 1970s. The more prominent systems included lithium/sulfurdioxide lithium-thionylchloride lithium-sulfurylchloride lithium-polycarbon monofluoride lithium-manganese dioxide and lithium-iodine Apologies to any chemistries that were not mentioned, but were studied and developed by the legions of scientists and engineers who worked on the many lithium battery couples during those early days. The 1980s brought many attempts to develop a rechargeable lithium battery; an effort that was inhibited by difficulties recharging the metallic lithium anode. There were occasional unfortunate events pertaining to safety (often an audible with venting and flame). These events were often due to the reactivity of metallic lithium (especially electrodeposited lithium with electrolyte solutions, but events were also attributed to a variety of other reactive conditions. Primary and secondary lithium batteries use non-aqueous electrolytes, which are inherently orders of magnitude less conductive than aqueous electrolytes. The reactions of the lithium electrode were studied extensively and this included a number of strategies to modify the reactivity of the Li-solution interface and thus improve its utility and safety [2].

2

Introduction

Studies of fast ion conduction in solids demonstrated that alkali metal ions could move rapidly in an electronically conducting lattice containing transition metal atoms in a mixed valence state. When the host structure is fully populated with alkali metal atoms - lithium ions in the most common context – the transition metal atom is in the reduced state. The structure is fully lithiated. As lithium ions are removed from the host, the transition metal (and host structure) is oxidized. A host structure is a good candidate for an electrode if (1) it is a mixed ionic-electronic conductor, (2) the removal of lithium (or other alkali metal ion) does not change the structure over a large range of the solid solution, (3) the lithiated (reduced) structure and partially lithiated (partially oxidized) exhibit a suitable potential difference versus lithium, (4) the host lattice dimension changes on insertion/removal of lithium are not too large, and (5) have an operational voltage range that is compatible with the redox range of stability for an accompanying electrolyte. This led to the development of rechargeable lithium batteries during the late 1970s and 1980s using lithium insertion compounds as positive electrodes. The first cells of this type appeared when Exxon and Moli Energy tried to commercialize the and systems, respectively. These were low voltage systems operating near 2 volts. In a large compilation of early research, Whittingham [3] reviewed the properties and preparation of many insertion compounds and discussed the intercalation reaction. The most prominent of these to find their way into batteries were and All of these systems continued to use metallic lithium anodes. The safety problems, real or perceived, limited the commercial application of rechargeable batteries using metallic lithium anodes. During that era Steele considered insertion compounds as battery electrodes and suggested graphite and the layered sulfide as potential candidates for electrodes of a lithium-ion battery based on a non-aqueous liquid electrolyte [4]. After the era of the transition metal chalcogenides came the higher voltage metal oxides (where M = Ni, Co, or Mn) [5,6]. These materials are the basis for the most commonly used cathodes in commercial lithium-ion cells. At about that time the concept of a lithium-ion cell was tested in the laboratory with two insertion electrodes cycling lithium ions between them, thus eliminating the use of a metallic lithium anode [7,8]. The next decade saw substantial research and development on advanced battery systems based upon the insertion and removal of lithium ions into host compounds serving as both electrodes. Much of the work was associated with finding a suitable material to host lithium ions as a battery negative. As mentioned before, the concept is not new: Steele and Armand suggested it in the 1970s [4,9,10]. Eventually, in 1991, Sony introduced the first commercial lithium-ion cell based on The cells had an open circuit potential of 4.2 V and an operational voltage of 3.6 V.

ADVANCES IN LITHIUM-ION BATTERIES

3

Since then, there has been an extraordinary amount of work on all aspects of the lithium-ion chemistry, battery design, manufacture and application. Indeed, the mention of a lithium-ion battery can imply dozens of different chemistries, both commercial and developmental as illustrated in Figure 1.

This book opens with an exhaustively complete chapter by Aurbach on the role of surface films in the stability and operation of lithium-ion batteries. His discussion lays the groundwork for the rest of the book because it puts many of the required properties of anode, cathode, solvent, salt, or polymer electrolyte into perspective in regards to their reactivity and passivation. Development of new electrolytes, anodes, and cathodes must account for this reactivity and indeed some new and promising electrode materials may continuously lose capacity due to their inability to passivate with the electrolytes employed. The discussion of materials' reactivity is followed by chapters on carbon (Ogumi Inaba) and manganese vanadate and molybdate anode materials for lithium-ion batteries. A brief chapter on oxide cathode materials by Goodenough gives a brief overview of current work on "traditional" lithium metal oxide materials and polyanionic compounds.

4

Introduction

Yamaki presents an extensive review of the extensive efforts in various laboratories to improve the electrolyte solvent systems and studies of their reactivity with anodes and cathodes. This chapter, combined with Aurbach's opening chapter, the chapter on temperature effects in lithium-ion batteries (Salomon, Lin, Plichta, and Hendrickson) and Broussely's chapter on aging mechanisms and calendar life predictions gives a comprehensive insight into the reactivity of the systems that constitute commercial cells. The chapters by Salomon, et al., and Broussely illustrate the limitations of the present commercial systems – limitations that are often ignored by application engineers using lithium-ion batteries in their appliances. Highlighting these operational limitations, which are functions of age, and operational and storage temperature, signals those working on materials and systems the type of shortcomings that must be overcome to improve the safety, reliability and utilization of lithium-ion batteries. Many think the future moves toward solvent free systems: Scrosati presents a chapter on polymer electrolytes, most of which are solventcontaining gel-polymers in practical systems, and Nishi discusses gel-polymer battery properties and production. Webber and Blomgren give extensive treatment of ionic liquids (otherwise known as ambient-temperature molten salts) and their use in lithium-ion and other battery systems. Scrosati's second chapter is on low-voltage lithium-ion cells: a variant of the chemistry which uses lower voltage couples (partially solving the anode material problem at the expense of system voltage and power. Several advantages are highlighted which illustrate the potential of these cells as replacements for 1.5 V systems. The final "material and chemistry" chapter is on electrochemical supercapacitors by Mastragostino, Soavi, and Arbizzani. The remaining chapters are "system" or "engineering" chapters. Thomas, Newman, and Darling present a thorough chapter on mathematical modeling of lithium batteries; Brodd and Tagawa describe Li-Ion cell production processes; Spotnitz explains the non-trivial nature of scale-up of LiIon cells; and van Schalkwijk explains the intricacies of charging, monitoring and control. This book, while intended for lithium-ion scientists and engineers, may have parts that are of interest to scientists from other fields: polymer electrolytes and ionic liquids are useful materials in systems other than batteries. Intercalation electrodes, perhaps not as we know them, but more as fluidized beds are finding use in sequestering contaminants from the environment. Researchers in those fields will benefit from much of the knowledge gleaned by those in search of a better battery. The editors realize that not every area of advanced research on lithium-ion batteries is represented in this book. However, it is hoped that

ADVANCES IN LITHIUM-ION BATTERIES

5

this book provides a timely snapshot of the current situation and with chapters extensively references, will serve as a reference volume that lasts comparatively long in this rapidly changing field. REFERENCES 1. 2.

3. 4. 5. 6. 7. 8. 9. 10.

W.S. Harris, Ph.D. Thesis UCRL-8381, University of California, Berkeley. KM Abraham and S.B. Brummer in Lithium Batteries, J-P. Gabano, ed., Academic Press, New York, 1983. M.S. Whittingham, Prog. Solid State Chem., 12, 41-111. B. C. H. Steele in "Fast ion transport in solids: solid-state batteries and devices" (North-Holland/American Elsevier, Inc., AmsterdamLondon/New York, 1973), p. 103. K. Mizushima, P.C. Jones, P.J. Wiseman, and J.B. Goodenough, Mat. Res. Bull., 15, 783, 1980. M.M. Thackeray, W.I.F. David, P.G. Bruce, and J. B. Goodenough, Mat. Res. Bull., 18, 461, 1983. M. Lazzari and B. Scrosati, J. Electrochem. Soc., 127, 773, 1980. D.W. Murphy, F.J. DiSalvo, J.N. Carides and J.V. Waszczak, Mat. Res. Bull., 13, 1395, 1978. M. Armand in "Fast ion transport in solids: solid-state batteries and devices" (North-Holland/American Elsevier, Inc., AmsterdamLondon/New York, 1973),, p 665. M. Armand in Materials for Advanced Batteries, D.W. Murphy, J. Broadhead, and B.C.H. Steele, eds., Plenum Press, New York, 1980.

1 The Role Of Surface Films on Electrodes in Li-Ion Batteries Doron Aurbach Department of Chemistry Bar-Ilan University Ramat-Gan 52900 Israel

1.0

INTRODUCTION

1.1

Passivation Phenomena in Electrochemistry

Surface film formation on electrodes is a very common phenomenon in electrochemical systems. Most metal electrodes in both aqueous and nonaqueous solutions are covered at a certain range of potentials with surface films that control their electrochemical behavior [1]. Most of the commonly used metals in electrochemical studies, as well as electrochemical devices, are naturally covered by oxide layers that may be formed spontaneously during their casting, due to the reaction of the bare metal with air oxygen [2]. Hydration of oxide films forms an outer layer of hydroxide, while reactions of oxides with air form an outer layer of carbonates. Surface films formed on metals comprised of oxides, hydroxides, and carbonates are electronically insulating, as they reach a certain thickness, but may be able to conduct ions: oxygen anions, protons and/or metal cations [3]. In spite of the huge diversity in the properties of metals, we can find a similarity in some properties of surface films formed on metals in terms of mechanisms and kinetics of growth, as well as transport phenomena and kinetics of ion migration through surface films. When a fresh active metal is exposed to a polar solution whose components may be reduced on the active surface to form insoluble metal salts, a surface film grows via a corrosion process. The driving force for this process is the difference between the redox potentials of the active metal and the solution species As a first approximation, we can assume a homogeneous surface film and Ohm's law, connecting the corrosion current density and Hence

Advances in Lithium-Ion Batteries Edited by W. van Schalkwijk and B. Scrosati, Kluwer Academic/Plenum Publishers, 2002

8

Surface Films in Lithium-Ion Batteries

where is the surface film's resistivity for electron tunneling (assuming homogeneous condition), and l(t) is its thickness (which grows in time). Assuming that all the reduction products precipitate on the active metal surface, then

K is the proportionality constant that depends on the molecular size of the surface species and their density of packing on the surface. Combining Equations 1 and 2, and integrating them with the boundary condition / = 0 yields:

which is the well-known parabolic growth of the surface films [4]. When the active metal exposed to solution is already covered by initial surface films, and hence at then:

We can assume that as the surface films formed on active surfaces in solutions reach a certain thickness, they become electronic insulators. Hence, any possible electrical conductance can be due to ionic migration through the films under the electrical field. The active surfaces are thus covered with a solid electrolyte interphase (the SEI model [5]), which can be either anionic or cationic conducting, or both. For a classical SEI electrode, the surface films formed on it in polar solutions conduct the electrode's metal ions, with a transference number close to unity. In most cases, the surface films on active metals are reduction products of atmospheric and solution species by the active metal. Hence, these layers comprise ionic species that are inorganic and/or organic salts of the active metal. Conducting mechanisms in solid state ionics have been dealt with thoroughly in the past [6-10]. Conductance in solid ionics is based on defects in the medium's lattice. Two common defects in ionic lattices are usually dealt with: interstitial (Frenkel-type) defects [7], and hole (Schottky-type) defects [8]. In the former case, the ions migrate among the interstitial defects, which may be relevant only to small metal ions. This leads to a transference number close to unity for the cation migration. In the other case, the lattice contains both anionic and cationic holes, and the ions migrate

ADVANCES IN LITHIUM-ION BATTERIES

9

from hole to hole [9]. The dominant type of defects in a lattice depends, of course, on its chemical structure, as well as on its formation pattern [10]. In any event, it is possible that both types of defects exist simultaneously and contribute to conductance. It should be emphasized that this description is relevant to single crystals. Surface films formed on active surfaces are much more complicated and may be of a mosaic and multilayer structure. Hence, ion transport along the grain boundaries between different phases in the surface films may also contribute to, or even dominate, conductance in these systems. The kinetics of the simplest solid electrolyte interphase (SEI) electrode should include three stages: charge transfer across the solution-film interface, ion migration through the surface films, and charge transfer in the film-metal interface. It is reasonable to assume that the ion migration is the rate-determining step. Thus, it may be possible to use the basic Equation 5 for ionic conductance in solids as the starting point [4,6,11]:

where a is the jump's half distance, is the vibrational frequency in the lattice, z is the ion's charge, W is the energy barrier for the ion jump, n is the ion's concentration, E is the electric field, and F is the Faraday number. When all of the potential falls on the surface films, then

where l is the film's thickness. At equilibrium zero, the exchange current is

In a high electrical field, obtained:

so the net current is

and thus a Tafel-like behavior is

In a low electrical field, Equation 8 can be linearized, and thus an Ohmic behavior is obtained:

where b is the analog of the Tafel slope extracted from Equation 8:

Hence, the average resistivity of the surface films can be extracted as

10

Surface Films in Lithium-Ion Batteries

where is the surface film resistance for ionic conductance, extracted from Equation 9, and I = iA. For example, the average resistivity values of surface films formed on active metals such as lithium magnesium and calcium in nonaqueous solutions are in the order of and respectively [4]. Hence, it appears that metal electrodes in solutions (which are covered by surface films) may behave electrochemically, similar to the usual classical electrochemical systems (Butler-Volmer type behavior. [12]).

1.2

Surface Films on Active Metal Electrodes Related to the Battery Field: Li, Ca, Mg

It is worthwhile and important to mention surface film phenomena related to Li, Ca, and Mg electrodes when dealing with the role of surface films in lithium ion batteries, because there are some similarities in the surface phenomena on active metal electrodes and lithium insertion electrodes in the electrolyte solutions commonly used in nonaqueous batteries. The surface chemistry of lithium, calcium, and magnesium electrodes in a large variety of polar aprotic electrolyte systems has been largely explored during the past three decades, and hence, the knowledge thus obtained may help in understanding the more complicated cases of the surface chemistry and surface film phenomena on lithium insertion electrodes used in Li-ion batteries. Figure 1 illustrates typical surface phenomena, which characterize active metal electrodes [13]. Initially, lithium, calcium, and magnesium are covered by a bilayer surface film comprised of the metal oxide in its inner part, and metal hydroxide and carbonates in the outer side, due to the inevitable reactions of the active metals with atmospheric components during their production (Figure la). As these active metals are introduced into commonly used polar aprotic solutions, there are replacement reactions in which part of the original surface films are dissolved or react nucleophilically with solution species. Solution species also percolate through the original surface films and react with the active metal (Figure 1b). This situation forms highly complicated and non-uniform surface films that have a vertical multilayer structure and a lateral mosaic-type structure on a sub-micronic, and even nanometric, scale (Figure 1c). The unavoidable presence of trace water in nonaqueous solutions further complicates the structure of these surface films (Figure 1d). Water hydrates most of the surface species such as oxides, hydroxides, halides, and active metal organic salts that percolate through the surface films and react with the active metal to form metal hydroxide, metal oxide, and possibly metal hydride, with hydrogen gas as the co-product (which evolves away from the surface) [14]. In the case of lithium, all of the relevant lithium salts formed as surface species and deposited as thin layers, in all relevant nonaqueous polar aprotic electrolyte solutions (e.g.,

ADVANCES IN LITHIUM-ION BATTERIES

11

Li halides, hydroxide, oxides, carbonate, Li alkyl carbonates, carboxylates, Li nitride, Li sulfide, etc.) conduct lithium ions. Hence, Li-ion can migrate through the surface films under an electrical field (see the SEI model [4,5]). As a result, lithium can be dissolved and deposited through the surface films, which cover the lithium electrodes, while their basic structure can be retained. In contrast, the surface films formed on calcium [15] and magnesium [16] in most of the commonly used aprotic electrolyte solutions cannot conduct the bivalent cations. Hence, dissolution of calcium and magnesium occurs via a breakdown of the surface films at relatively high over-potentials (Figure 1e [15,16]), and Ca or Mg deposition in a large variety of commonly used nonaqueous electrolyte solutions is impossible. In fact, there is no evidence of possible electrochemical calcium deposition from any nonaqueous solution. In the case of magnesium, it is possible to achieve a situation in which Mg electrodes are not passivated by stable, robust surface films. This is the case of ether solutions containing Grignard salts (RMgX) or complexes of the type (A = Al, Br, X=halide, R=an organic group such as alkyl) [17]. In the latter solutions, Mg can be dissolved and deposited reversibly. However, generally speaking, even in the case of Li electrodes, intensive active metal dissolution processes lead to the breakdown and repair of the surface films. The non-uniformity of the surface films leads to non-uniform secondary current distribution, which leads to a very non-uniform electrochemical process. Hence, when metal is dissolved selectively at certain locations, the surface films are broken down and fresh active metal is exposed to solutions species, with which it reacts immediately (which leads to the "repair" of the surface films and increases further non-uniformity). The expected nonuniform structure of the surface films leads to the dendritic deposition of lithium in a large variety of electrolyte solutions, as illustrated in Figure 1f. The surface chemistry of lithium electrodes in a large variety of electrolyte solutions has been intensively explored in recent years [18-24]. These studies have definitely paved the way for understanding the surface chemistry of lithiated carbon anodes for Li-ion batteries and for the identification of important surface species, which are formed on Li-C electrodes. The surface chemistry of calcium and magnesium was also explored [15, 16], but these studies are, in fact, irrelevant to the field of Li-ion batteries. Intensive studies of lithium electrodes by impedance spectroscopy [25] and depth profiling by XPS [26,27] have clearly indicated the multilayer nature of the surface films formed on them. It is assumed that the inner part, close to the active metal, is compact, yet has a multilayer structure, and that the outer part facing the solution side is porous. Some evidence for this assumption was found by in situ imaging of lithium deposition-dissolution processes by atomic force microscopy (AFM) [28]. There is also evidence that the inner part of the surface films is more inorganic in nature, comprised of

12

Surface Films in Lithium-Ion Batteries

species of a low oxidation state (due to the highly reductive environment, close to the active metal surface), while the outer parts of the surface films on lithium comprise organic Li salts [18,19,16,27,29]. These studies also serve as an important background for a better understanding of the electrochemical behavior of lithiated carbon electrodes.

ADVANCES IN LITHIUM-ION BATTERIES 1.3

13

Noble Metal Electrodes Polarized to Low Potentials in Lithium Salt Solutions

We found that noble metal electrodes (e.g. Au, Pt) polarized to low potentials in nonaqueous Li salt solutions develop surface chemistry, surface films, and passivation phenomena, which are very similar to those developed on lithium electrodes in the same solutions [30,31]. In fact, when the noble metal electrodes are polarized to sufficiently low potentials in solutions of alkyl carbonates, esters, and ethers that contain lithium salts, the solvents, the atmospheric contaminants and the salt anions etc.) are reduced to form insoluble Li salts (e.g., RCOOLi, ROLi, LiOH, LiF, LiCl), quite similar to the Li salts formed by reduction of these solution species by Li metal. However, the scenario of the surface film formation on noble metals may be different than that related to lithium metal. When a lithium electrode is in contact with the solution, the solution components are exposed to a very non-selective, highly reducing power of the Li surface. As the surface films grow, they progressively block the possibility of electron transfer from Li to the solution species, and hence, the selectivity of the reduction of solution species and the build-up of the surface films increases gradually as the surface films grow. This obviously leads to the multilayer structure of the surface films formed on Li electrodes in solutions. In the case of noble metal electrodes, their polarization to low potentials, either potentiostatically or galvanostatically, leads to a gradual and highly selective reduction of solution species, depending on the potentials that the electrode reaches. Figure 2 shows a typical example of the various processes that take place when a noble metal electrode is polarized cathodically and anodically in a polar aprotic solution containing a Li salt [32]. It should be noted that the study of noble metal electrodes in nonaqueous Li salt solutions is even more relevant to the understanding of the behavior of lithiated carbon anodes because, in the latter case, the carbon electrodes that are initially nearly surface film-free, are also polarized from OCV see also Figure 2) to low potentials in the course of Li intercalation, and surface films are gradually formed on the carbon electrode as it reaches lower potentials. Hence, the order of surface reactions may be similar to that described in Figure 2, except for the Li under potential deposition and stripping processes, which are irrelevant to carbon electrodes (into which lithium is inserted at potentials higher than that of Li deposition).

14

Surface Films in Lithium-Ion Batteries

2.0

THE SURFACE CHEMISTRY OF Li, AND CATHODICALLY POLARIZED NOBLE METALS IN Li BATTERY ELECTROLYTE SOLUTIONS

2.1

Classification of Reactive Components: Solvents, Salts, Atmospheric Contaminants and Additives

The nonaqueous solvents that are commonly used in electrochemistry can be classified as follows [33]: 1. Ethers These include diethyl ether; members of the 'glyme' family, namely, polyethers of the type (e.g., dimethoxyethene for n=l), cyclic ethers such as tetrahydrofuran (THF) and 2-methyl tetrahydrofuran; and cyclic acetals such as 1-3 dioxolane.

ADVANCES IN LITHIUM-ION BATTERIES

15

2. Esters These include methyl formate, methyl and ethyl acetate, and 3. Alkyl carbonates These include cyclic compounds such as butylene, propylene, and ethylene carbonates (BC, PC, EC), and linear compounds such as dimethyl, diethyl carbonates, ethyl-methyl carbonate, etc. (DMC, DEC, EMC). 4. Inorganic Solvents The most common inorganic solvents used in batteries were (thionylchloride), and (sulfuryl chloride). The former solvent was used in both secondary and primary Li battery systems, while the latter could only be used in primary Li batteries [34]. 5. Miscellaneous Solvents such as acetonitrile, nitromethane, N,N-dimethyl formamide, dimethyl sulfoxide, sulfolane, and methyl chloride are also often used in nonaqueous electrochemical studies.

It should be noted that the solvents in groups 2, 4 and 5 are irrelevant to the field of Li-ion batteries due to the limited electrochemical windows of some of them, problems of electrode surface reactivity with them, and the lack of electrode passivity in some of these solvents. The ethers (group 1) are also problematic, since their oxidation potentials are too low for 4 V Li-ion batteries. Hence, the most suitable solvents for Li-ion batteries remain the alkyl carbonate (group 3 above) [3]. However, the high polarity of the alkyl carbonate solvents automatically means high reactivity at low potentials. These solvents are indeed readily reduced at potentials below 1.5 V (vs. in the presence of Li-ions [30,32]. The apparent stability of lithium or lithiated carbon electrodes in alkyl carbonate solutions is because of passivation phenomena of these electrodes, as described later. Solvent and electrolyte properties are discussed further in Chapter 5, Liquid Electrolytes. In recent years, there has been an increasing interest in the use of solid electrolyte matrices for Li and Li-ion batteries. From the point of view of surface chemistry and surface film formation, we can divide the polymeric matrices connected to the field of Li batteries into two categories: 1. Gel electrolytes [35]. The polymeric matrix includes base polymers that do not interact with Li salts such as polyacrylonitrile, polyvinylidene-difluoride (PVdF), etc.; plasticizers that are usually alkyl carbonate solvents (e.g., EC, PC); and lithium salts. It should be noted that compounds with C-F bonds such as PVdF react with both Li and lithiated carbons to form carabides and LiF. However, in the case of the commonly used gel electrolytes, the reactions of the alkyl carbonates in the matrices dominate the electrodes' surface chemistry.

16

Surface Films in Lithium-Ion Batteries

2. Solvent-free matrices Here, the polymeric species are designed to interact with Li salts, leading to the necessary ionic separation for electrolyte systems, and therefore, the presence of liquid solvents can be avoided. In order to obtain dissolution of Li salts, the polymers have to contain ethers, ester or other polar groups. Indeed, the most important polymeric electrolytes of this kind are based on polyethylene oxide and its derivatives [36-40]. These polymers have the reactivity of ethers towards Li and lithiated carbon surfaces, which is much lower as compared with that of alkyl carbonates. However, since battery systems with solid-state electrolyte matrices are usually operated at elevated temperatures (>60 °C), it is obvious that there are surface reactions between the polyethers and the lithiated carbons which form of surface films. We should also mention problems of limited electrochemical windows when using solvent-free polymeric electrolytes, since the oxidation potentials of polyethers are similar to those of ethers which are usually in the 4-5 V range (vs. Polymer and gel electrolyte systems are discussed in Chapters 7 and 8 by Nishi and Scrosati, respectively. Ionic liquids (ambient temperature molten salts) are discussed in Chapter 6. The second component is, of course, the Li salts. The list includes

and, recently, the new salt from Merck, (LiFAP) [41]. On examining the various Li salts available, we find that is the most commonly used salt, so far, in Li-ion batteries because it is non-toxic, non-explosive, and highly soluble in nonaqueous solvents, thus forming highly conductive electrolyte solutions. In addition, it is apparently stable with both cathode and anode materials at a wide temperature range. All the other salts in the above list have disadvantages that make them less attractive than for use in Li-ion batteries. For instance, may be explosive, is considered to be too poisonous (arsenic), solutions have too low a conductivity, and the salts containing the (fluorinated) groups may be too expensive and their thermal stability limited. It should be noted that all the anions of the above salts are reactive with lithium and lithiated carbons, and hence, their reaction with the electrodes may influence their surface chemistry considerably. The third group of active components is obviously the reactive atmospheric gases. All nonaqueous solutions contain unavoidable traces of and All of these gases are reactive with lithium and lithiated carbon. Their surface reactions form Li oxides, Li nitrides, Li hydroxide, and Li carbonate, respectively [42]. We should add to this list of contaminants the decomposition products of This salt decomposes to LiF and (an equilibrium reaction) [43]. The latter compound readily hydrolyzes to form HF and Hence, solutions always contain HF. HF reacts with both electrodes and basic surface species to form surface LiF as a major solid product.

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17

The last group of reactive components to be mentioned is the various solution additives which were suggested for improving solution properties, electrode passivation, and for obtaining unique features such as overcharge protection and enhanced safety. In this respect, we can mention solvents such as halogenated alkyl carbonates, [44,45] sulfur-containing solvents (e.g., ethylene sulfite) [46,47], polymerizing agents such as vinylene carbonate [48], organo boron complexes [49], and inorganic compounds (CO2 [50], SO2 [51], nitrates [52],). The use of additives for the modification of the surface chemistry of electrodes in Li-ion batteries will be dealt with in depth later in this chapter (see Section 5.3). 2.2

Basic Reactions of Nonaqueous Electrolyte Solutions on Li and Li-C Surfaces and on Carbon and Noble Metal Electrodes Polarized to Low Potentials

A great deal of effort has been invested in recent years in the study of the surface chemistry of lithiated carbon anodes in Li battery electrolyte solutions. Fortunately, the basic surface reactions of a large variety of nonaqueous Li salt solutions on Li, Li-C, and noble metal electrodes polarized cathodically are very similar. The tools for the study of the surface chemistry of these systems included XPS [53], AES [54], FTIR [55], Raman [56], EDAX [57], and, recently, SIMS-TOF [58]. The study of the surface chemistry of the composite electrodes used in Li-ion batteries is difficult. Hence, a previous study of the surface chemistry developed on noble metal and Li electrodes in the solutions of interest may be very helpful. It should be emphasized that the use of XPS, AES, Raman (laser beam needed), and SIMS-TOF may lead to changes in the surface species during the measurements due to further surface reactions induced by X-rays, laser beams, or bombardment by ions. Surface sensitive FTIR spectroscopy is, so far, the best non-destructive surface-sensitive technique that can provide useful and specific information. While the study of the surface chemistry of Li or noble metal electrodes requires the use of methods such as external or internal reflectance, the study of the composite electrodes used in Li-ion batteries requires the use of the highly problematic diffuse reflectance mode (DRIFT) [59]. Because of that, the study of surface films formed on carbon electrodes can benefit so much from preceding studies of the surface films formed on lithium or noble metal electrodes in the same solutions. Figure 3 shows a typical FTIR analysis of the surface films formed on graphite electrodes in a methyl-propyl carbonate(MPC) solution, which is based on FTIR spectra of a higher resolution obtained from lithium electrodes treated in the same solution and some reference solutions (external reflectance mode) [60]. Spectrum 3a relates to surface films on a graphite electrode cycled in an MPC solution. Spectrum 3b relates to surface films formed on lithium in the

18

Surface Films in Lithium-Ion Batteries

same solution. This spectrum (external reflectance mode) is of a higher resolution than that of the graphite particles (3a, diffuse reflectance mode). With the aid of two more reference spectra, from surface films formed on lithium in DMC solutions containing methanol (3c), and from a thin film of on lithium (3d), it was possible to conclude that the surface films formed on graphite in MPC are composed of all the possible reduction products of the solvent. These include Figure 4 shows FTIR spectra measured from graphite electrodes treated in ECbased solutions (including as an additive in one case), and an FTIR spectrum of the major expected surface species formed, [61]. The latter species was isolated by electrolysis of EC in a solution followed by precipitation in a Li salt solution. These spectral studies clearly show that in EC-based solutions, is a major surface species formed on carbon electrodes. When the solutions contain is also formed as a major surface species. Figures 3 and 4 demonstrate that surfacesensitive FTIR spectroscopy serves as a very useful tool for the analysis of surface reactions of Li-ion battery electrodes, as well as the importance of the use of reference measurements (e.g., studies of Li and noble metal electrodes treated in the same solutions).

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19

20

Surface Films in Lithium-Ion Batteries

ADVANCES IN LITHIUM-ION BATTERIES 21

22

Surface Films in Lithium-Ion Batteries

Figure 5 is a schematic representation of major aspects of the surface chemistry of graphite electrodes in electrolyte solutions containing EC as a major component, based on rigorous FTIR and XPS spectroscopic studies [62]. Table 1 provides surface analysis of graphite and lithium electrodes in a large variety of commonly used electrolyte solutions. The major surface species that comprise the surface films formed on the active electrodes in the solutions specified, are presented. Schemes 1 and 2 describe the surface chemistry of Li and Li-C electrodes in EC- and PC-based electrolyte solutions. Scheme 3 describes the surface reactions of the Li and Li-C electrodes in ester-based solutions. Scheme 4 relates to the surface reactions of ethers with Li and Li-C electrodes. Scheme 5 describes selected surface reactions of commonly used salt anions in Li and Li-ion batteries. Finally, Scheme 6 shows possible surface reactions of CO2 on Li and Li-C electrodes. Table 3 (at the end of the chapter) provides a list of references for the various surface studies described in Figures 2-5, Table 1, and Schemes 1-6 [29,42,50,53,58, 60-73]. We should note that in addition to the above-described surface chemistry, there are reports in the literature on the formation of polymeric species on lithiated carbon electrodes in alkyl carbonate solution. These polymers may include polyethylene (due to polymerization of the ethylene formed by EC reduction), and polycarbonates (due to polymerization of cyclic alkyl carbonates such as EC) [58,63]. Scheme 1: Possible reduction patterns of alkyl carbonates on Li

ADVANCES IN LITHIUM-ION BATTERIES Scheme 2. EC (PC) reduction mechanisms (nudeophilic paths). The expected reaction

Has no evidence from surface studies

In a separate study, a nucleophilic attack on EC:

Hence, another reduction mechanism of EC (or PC) on active electrodes can be:

23

24

Surface Films in Lithium-Ion Batteries Ester reaction schemes

ADVANCES IN LITHIUM-ION BATTERIES Scheme 4: Ether reaction patterns

25

Surface Films in Lithium-Ion Batteries

26

Scheme 5. Surface reactions of commonly used Li salts.

Scheme 6. Possible

reaction patterns

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3.0

SURFACE CHEMISTRY OF CARBON ELECTRODES

3.1

Classification of Carbon Materials in Terms of Li Insertion

27

There are a large variety of carbonaceous materials that can interact with lithium ions in solutions and serve as Li insertion anodes in Li-ion batteries. The behavior of the lithium insertion processes into carbons in terms of capacity, stability, kinetics, and potential profile, depends very strongly on their 3D structure and morphology. Indeed, this chapter deals with the surface chemistry of electrodes, and hence, cannot deal in depth with structural aspects of carbonaceous materials. However, it was found and clearly demonstrated that the surface chemistry of carbons, and especially their surface film related stability, depends very strongly on their 3D structure. Therefore, in this section we deal with some structural aspects of carbonaceous materials. Figure 6 presents a scheme of major classes of carbons, which are currently studied in connection with Li-ion battery systems. These include graphite materials that are highly ordered and are composed of graphene planes packed in parallel, [74] between which Li-ions are intercalated. Another type of ordered carbon that was recently studied in connection with Li insertion was the carbon nanotube (either single or multiwall structure) [75,76]. The other two major classes are disordered carbons that may be either soft and graphitizable [77-80] or hard and non-graphitizable [81-85]. The graphitic materials suggested as anode materials appear as flakes [86,87], beads [88-90], fibers [91-92], and chopped fibers [93]. Figure 7 presents SEM micrographs of selected carbonaceous materials of different 3D structure and morphology. Figure 8 shows illustrations of the morphology of several types of graphitic materials that are currently used as anode materials in Li battery systems. We should emphasize some points regarding the 3D structure and morphology of carbonaceous materials that are important to the field of Liion batteries: 1. Graphitic carbons can insert Li up to a stoichiometry of corresponding to The process is intercalation: Li-ions occupy sites between graphene planes. 2. Graphitic carbons can appear in a variety of shapes and morphologies, as demonstrated in Figures 7 and 8 (flakes, beads, fibers, etc.). The morphology of the graphitic materials may have a strong impact on their electrochemical behavior.

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Surface Films in Lithium-Ion Batteries

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29

In general, graphites are the carbon material most sensitive to the solution composition, in terms of reversibility and stability (in Li insertion processes). As discussed in depth in the next section, the stability of graphite electrodes in Li insertion processes depends on surface film formation and passivation phenomena. The morphology of the graphite particles strongly influences critical stages in the precipitation of the surface films and their passivation properties. In general, when the graphite particles have some degree of disorder (either turbostratic or in orientation of the crystals comprising the particles), their reversibility and stability in Li insertion processes is higher and their performance is less dependent on the solution composition, as compared with highly ordered materials. 3. Disordered carbons may insert lithium at a higher capacity than that of

graphite. The mechanisms for Li insertion into disordered carbons are complicated and cannot be considered as a simple intercalation [94-95]. There are several types of Li insertion sites in disordered carbons [96]. Part of the capacity is due to adsorption type processes [97], and part of the Li insertion may involve interactions with C-H bonds [98-99]. These complications may lead to intrinsic irreversibility in Li insertion processes into disordered carbons. 4. The impact of the surface chemistry on the performance of disordered

carbons is much less important as compared with the case of graphite. Some destruction mechanisms that relate to surface reactions of the carbons with solution species that exist in graphitic materials [64] are irrelevant to disordered carbons. This is because the existence of disorder in carbonaceous materials adds some intrinsic stability to their structure (as compared with the highly ordered graphitic carbons).

30 3.1

Surface Films in Lithium-Ion Batteries The Anodes and Cathodes in Li-Ion Batteries Are Composite Electrodes

The cathodes are dealt with in depth in Section 7 of this chapter. However, there are some common morphological features of both anodes and cathodes that justify a comparative discussion. As such, some of their properties related to their morphology are dealt with in this section. Both the anodes and the cathodes used in Li-ion batteries are composite electrodes. Carbon anodes include the active mass, which may comprise more than one type of carbon particle; (>90%) polymeric binder such as Teflon, or polyvinylidene difluoride PVdF (85%), and a polymeric binder (